Cellulose esters and ethers plasticized with 1.6 hexandiol di-2-ethyl hexoate



Dibut-ylitart-rate cELLULosE ESTERS AND ET ERs PLASTICIZED WITH 1.6 HEXANDIOL nmsrnrr HEXOATE Charles P. Albus and Richard E; Field, Easton, Pa., as-

signers to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawings Application November 16, 1951, Serial No. 256,815 1 Claim. or. 106-180) This invention relates particularlyjto lower alkyl cellulose esters and ethers plasticized with di-Z-ethyl hexanoic acid di-esters of 1,6-heXanediol In the preparation of cellulose esters for various uses, it is common practice in the an to modify them by the addition of materials having a. plasticizing or softening action. it is a necessary requisite; ofthese. plasticizers that they be compatible over a: fairly wide range. have good stability, low volatility, good resistance to oxidation or migration on aging, be resistant to the leaching action of The foregoing esters have not been accepted with com i plete satisfactiom however, because of their various occurs only after the molded article or cast film is allowed to stand for some time. In either case, the cellulose ester reverts to its original hardness and brittleness. 7

Low boiling plasticizers evaporate slowly on standing at room temperature or at temperatures to. which the cellulose ester is subjected either in preparation or use. As a result, the cast'filrnor molded'articl'e again. becomes brittle and may easily crack or break. Films, lacquers, and molded articles. may besubjectedto water in their use. If the plasticizer is Water soluble to, even a small extena the plastici'zr. ifs 'leachd out. of" the. cellulose ester which then 'be'com s hard and brittle. Other properties i which may be deslredfot' a plasticizer will, depend onthe end. use of the cellulose ester or ether. Some. plasticizers will impart resistance to flammability, cold', oils greases,

and weathering/some Plasticizers discolor badly or oxidize to give; ofl, objectionable odors, No. one' plasticizer seems, torble, acu're-aIl fO i defects. in use. This is probably. the. reason, why'sciveral hundred plasticizers haveibeen; suggested. Thefrnajority. orme howev r,

Trialcetin} (.glycerylztiiacetatei) Bis rnethoxyethyh adipate Methoxyethyl oleate Triphenyl phosphate, Tricresyl phosphate Methylphthalyl ethyl glycolate Diniethyl phthalate f Bis-methosyethylphthalate" Bis-b i xyethy ph h hutoxyejthyl stearate Fish Gil,

ot nsee oilf rinseedg i Soybean oil defects. Triacetiri and dibu'tyl tartrate have poor wa ter resistance. Bis-methoiryethyl adipate is both water sensitive and rather volatile; Methoxyethyl oleate and butoxyethyl stearate seem to be rather volatile and have been found toexude from cellulose acetate filmsimmersed in water. Triphenyl phosphate has pjoor light stability and is likely to cause discolora'tion of cellulose'acetate and nitrocellulose. Tficresylphosphate has poor light as bility and also has the added defect or being rather especially if a large portion of the ortho isomer Which is believed to be the? toxic element present. Methyl phthalyl ethyl glyc'olate appears to beraithe'r volatile and water sensitive. It is also incompatible with cellulose acetate of 52% combined acetic acid content. Dimethyl p'hthalate is rather volatile; and has' a" tendency at low temperatures to crystallize from films and other articles not only causingembrittl'ement but also a possibly'p'artially' permanent loss of transparency andwhitenisis-m'ethoxy'ethyl and bis-.butoxyethyl phthalate appear to be fairly volatile when used as plasticizers for cellulose esters. Fish and cottonseed oils possess: objectionable odors and are likely to become rancid on aging", Vegetable oils, suchas linseed and soybean, have limited compatibility in ethyl cellulose and readily exud'e when more than about 30 to 40% is incorporated as a plasticizer. V p

V lthas been foundthat the foregoing, objectionsfhave been irra large measure. overcome by plasticizing cellulose. ester and ether compositions with di-e sters of ali phatic monocarbonylic' acids of 2 to 18 carbon atoms and 1,4-butanediol' or l d heiranediol. p p Z Aliphatic monocarboxylicacid diresters of l,4-hutanediol and 1,"6-hex anediol arelreadily compatible with the various celluloseesters and ethers andi do not exude or show migration of plasticizer on standing when used as plasticizers "for cellulose esters and others .They

impart outstanding flexibility; toughness, resistanc'egto Water, dimensional stability inwater, etc, to cellulose esters and ethers. Theyare' unaifected by ultraviolet light and do not become discolored on egtposure to sun light. They are stalile'to heat and"'sho'w improved resistance: to volatiliz-ing frornvcellulose ester andether compositions exposed to" heat. in manufactureior use. They are: odorless and; do not impart-objectionable odors to cellulose. esterand ether. compositions. 1 e

'l ,4*-butanediol;. HOH2-GH2CH2CH2OHg and 1,6"- hexanediol', H@H2C-'CH2 CH2CH2C& CH2OH; are commercially availableproducts; The" former. is-prepared by catalytic hydrogenation" of 2 butyn-l,4-diol which is obtained: from. thereaction of acctylenewwith formaldehyde and the latter isobtained fromthe dinr'erization of propargyl alcohol, yielding.2,4-hexadiyne-1,6-diol followed by catalytic hydrogenation.

The following are illustrative examples of saturated aliphatic. monocarboxylic. acids: having the general J structure;.;.Qn l-Izn.+l. COOH', which may bev employed in e'sterifying; .IATbutanediOl: and ll,6-hexanediol to form di-esterssuitable asplasticizers for cellulose esters and ethers: I

Unsaturated acids, such as oleic and ricinoleic acid, may also be employed.

The aliiihatic monocarboxylic acids maybe used albne or amixture of two aliphatic monocarboxylic acids may Patented Apr 17, -19 56- 3 be used to prepare esters useful as plasticizers for cellulose esters and ethers. -It is'believed that better compatibility and improved physical properties will result from the use of mixed. aliphatic monocarboxylic acid di-esters of 1,4-butanediol' and of 1,6-hexanediol.

The resulting esters will then have the following general formulae:

wherein R is the residue of an aliphatic monocarboxylic EXAMPLE I 1,6-hexanediol dibutyrate 59 parts of 1,6-hexanediol and 158 parts of pyridine were charged into a 500 ml., 3-necked flask, equipped with stirrer, thermometer, reflux condenser, and dropping funnel, and the mixture heated to reflux. 106 parts of n-butyryl chloride were added dropwise to the refluxing mixture during a period of 1 hour. The stirring was continued for 2 hours after the addition was complete. The reaction mixture was then poured into ice water and concentrated hydrochloric acid added in a sufficient quantity to give a pH of 5. The organic material was extracted with 200 parts of ether and the extract washed with 10% sodium carbonate solution and then with water. After removal of the ether, the ester was distilled as a colorless liquid with a boiling point of 112-114 C. at 2 mm. pressure.

v EXAMPLE II 1,6-hexanedi0l di-2-ethylhexoate 59 parts of 1,6-hexanediol, 144 parts of 2-ethylhexoic 'acid, and 5 parts of 50% sulfuric acid were charged into a 500 ml. flask, equipped as in Example I. The mixture was refluxed for 2 hours and the water removed as it formed. The refluxing and water removal was continued for an additional 2 hours. The reaction mixture was then washed with 10% aqueous sodium carbonate solution and finally with water. Fractionation yielded the ester product as a light yellow liquid having a boiling point of 1.57-160 C. at 0.5 mm. pressure.

EXAMPLE III 1,4-butanediol a'ilaurate 45 parts of 1,4-butanediol. 200 parts of lauric acid, aha 3 parts of 50% sulfuric acid were charged into a 500 ml.

flask, equipped with stirrer, thermometer, take-01f condenser, and inlet for dry, oxygen-free nitrogen. After purging with nitrogen, the reaction mixture was heated at 120-150 C. for 4 hours. The water as it was formed was removed by distillation. The reaction mixture was then heated in vacuo at ISO-200 C. and 1.5 mm. for 1 hour to remove all volatile matter. The non-distilled residue which is the ester is a yellow pasty solid.

EXAMPLE IV I 1,4-butanediol diacetate dride, 60 parts of acetic acid (glacial), and, 1.5 parts of sodium acetate (anhydrous) were charged into a 500 ml. flask, equipped as in Example I. The mixture was heated at reflux for 4 hours and thereafter heated under reduced pressure to remove the acetic acid. The reaction mixture was then washed with water, dried, and fractionated. The diacetate was obtained as'a water-white liquid having a boiling point of 62-65 C. at 1.5 mm. pressure.

EXAMPLE V 1,4-butanediol di-Z-ethylhexoate 45 parts of 1,4-butanediol and 158 parts of pyridine were charged into a 500 ml. flask, equipped as in Example I, and the mixture heated to reflux. 162 parts of Z-ethylhexanoyl chloride were added dropwise to the refluxing mixture during 1% hours. The reaction mixture was stirred for an additional 2 /2 hours at room temperature and worked up as in Example I. Fractionation gave a colorless liquid product having a boiling point of 148- 152 C. at 0.4 mm. pressure.

EXAMPLE VI 1,4-butanediol acetate stearate parts of 1,4-butanediol and 284 parts of stearic acid were heated at 200 C. for 4-5 hours, removing the water by distillation as it was formed. The reaction mixture was cooled to room temperature and 102 parts of acetic anhydride added. The mixture was then heated to 200C. during 3 hours, distilling ofi acetic acid and excess acetic anhydride. The mixture was finally vacuum stripped at ISO-250 C. and 1-5 mm. to remove any volatiles. The residue was the desired product.

EXAMPLE VII 1,6-hexanediol acetate stearate Example VI was repeated with the exception that 90 parts of 1,4-butanediol were replaced by 118 parts of 1,6-hexanediol.

The esters prepared above are readily compatible with the cellulose esters and ethers commercially used, such as cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose nitrate, cellulose nitrate acetate, ethyl cellulose, benzyl cellulose, and the like. The esters may be incorporated into molding powders of cellulose esters and ethers or into solutions which are normally prepared for films, lacquers, dopes, and laminating solutions. The concentration or amount to be used as a plasticizer will depend on the type of cellulose ester or ether composition and the properties desired of the cellulose ester. The most eificacious amount to be employed for any particular composition can be very readily'determined by simple, routine spot experiments. In general, however, the amount of plasticizer to add for molding powders may range from 20 to 40% of the powder, in solutions for films anywhere from 5 to 30%, in lacquers about 5 to 50%, in dopes from 10 to 100%, and in laminating solutions from 10 to 30%. All of these percentages are based on the weight of the cellulose ester or ether.

The following examples illustrate the application of the foregoing esters as plasticizers and the improved results obtained thereby when compared with currently used plasticizers.

EXAMPLE VH1 A film of cellulose acetate of 5 mil thickness, containing 58.4 to 59% combined acetic acid, was prepared by casting the composition given below containing various commercial plasticizers on a clean, glass plate with a doctor blade, followed by air drying for 48 hours at room temperature at a controlled rate to prevent blushing of or other physical damage to the film. The film was then removed from the glass plate and further dried for 2 hours at 60 C. in the presence of freely circulating air.

ag'tcererr Harts: Cellulose acetate 15' Plasticizer 3 Methylenechloridenu 50. Ethylene chloride 22 Absolute ethanol.

TABLE 1 Percent Weight Loss of Film After 24 Hours at 100 C.

Plasticizer Triacetin Dibutyl tartrate- Methoxyethyl oleate. Butoxyethyl stearate 1 Bis-methoxyethyl adipate 1,4-Butanedlol (liphenoxyacetate 1,5-Pentanediol dicyclohexylacetate 1,4-Butsnedlol diacetate 1,4-Butanediol di-Z-ethylhexanoat 1,6-Hexanedlol di-Z-ethylhexanoate.

999-9 9 5 9 98? unmaeiwtummol- 1 Plesticizer not completely compatible.

EXAMPLE IX In like manner, a 5 mil thick film of cellulose acetate was prepared as given in Example VI in which 1,6-hex- :anediol dibutyrate was substituted for various commonly used commercial plasticizers in the following composition:

Parts Cellulose acetate Plasticizer 3 Methylene chloride 50 Ethylene chloride 22 Absolute ethanol 10 Samples of all of these films were completely immersed in water at room temperature for 48 hours, removed, rinsed with distilled water, and dried for 2 hours at 60 C. The samples were then weighed, and the per cent weight loss of the films was determined. The results obtained are given in Table 2, which clearly shows the superior resistance of 1,6 hexanediol dibutyrate to the leaching action of water over prior art and various commonly used plasticizers.

1 Plasticizer exuded; film became hazy. 1 Plasticizer not completely compatible.

6 EXAMRLE' X Ethylene chloride 7 Abs u e h no In like manner, films of the same thickness were prepared in which the plasticizers prepared as described above were substituted for the various commercial plasticizers in the given composition. Fihns of excellent flexibility, toughness, and clarity were produced.

Samples of all of "these films were exposed to freely circulating air in an oven for 24 hours at 100 'C. following which the per cent weight was determined. The superiority of films containing the plasticizers of this invention over those containing various prior art and commonly used commercial plasticizers in resistance to weight loss under these conditions is shown in Table 3.

TABLE 3 Pfirccntfgight ass 0 m Plasticizer After 24 Hours at 100 C.

Triacetin 9. 7 4 0 Dibutyl tartrate- 9. 8 Methoxyethyl oleate 9. 9 Butoxyethyl stearate 1 8.1 Bis-methoxyethyl adipate... 14. 5 Bis-butoxyethyl phthalate 7. 8 1,4-Butanediol Diphenoxyacetate 7.8 1,5-Pentanediol dicyclohexylacetate 8. 0 1,4Butanedio1 diacetate 7. 5 l 5 1,4-Butaned1ol dllaurate 5. 2

1 Plasticizer not completely compatible.

EXAMPLE XI A film of cellulose acetate butyrate of 5 mil thickness having an average acetyl content of 30% and butyryl content of 17.5% was prepared as given in Example IX containing various commonly used commercial plasticizers from a composition consisting of the following:

Parts Cellulose acetate butyrate 15 Plasticizer 3 Methylene chloride 50 Ethylene chlori 22 Absolute ethanol 10 Similar films were prepared in which the plasticizers of this invention were substituted for the various commercial plasticizers.

Samples of all of these films were completely immersed in water at room temperature for 48 hours, removed, rinsed with distilled water, and dried for 2 hours at 60 C. The samples were then weighed, and the per cent weight loss of the films was determined. The results obtained are given in Table 4 and clearly show the superior resistance of the plasticizers of this invention to the leaching action of water over various prior art and commonly used plasticizers.

Acomposition of matter comprising an organic cellulose derivative selectegl fr om the class consisting of Water-in- 8 soluble cellulose esters of lower alkyl monocarboxylie acids and mixtures thereof and water-insoluble cellulose ethers. of lower alkyl monohydric alcohols containing, in.

a plasticizing amount, 1,6-hexanediol di-2-ethylhexoate.

References Cited in the file of this patent UNITED STATES PATENTS 598,648 Schupphaus Feb. 8, 1898 1,084,702 Machund Jan. 20, 1914 2,017,070 Lazier Oct. 15, 1935 2,129,156 Trolander Sept. 6, 1938 2,341,464 Meyer Feb. 8, 1944 2,549,050 Brophy et a1 Apr. 17, 1951 2,578,684 Filachione Q Dec. 18, 1 951 2,592,234 Be1l Apr. 8, 1952 I FOREIGN PATENTS 

